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A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts

Nature volume 553, pages 323–327 (2018)Cite this article

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Abstract

The oxygenation of the deep ocean in the geological past has been associated with a rise in the partial pressure of atmospheric molecular oxygen (O2) to near-present levels and the emergence of modern marine biogeochemical cycles1,2,3,4,5. It has also been linked to the origination and diversification of early animals3,5,6,7. It is generally thought that the deep ocean was largely anoxic from about 2,500 to 800 million years ago1,2,3,4,5,6,7,8,9,10,11,12, with estimates of the occurrence of deep-ocean oxygenation and the linked increase in the partial pressure of atmospheric oxygen to levels sufficient for this oxygenation ranging from about 800 to 400 million years ago3,5,7,11,13. Deep-ocean dissolved oxygen concentrations over this interval are typically estimated using geochemical signatures preserved in ancient continental shelf or slope sediments, which only indirectly reflect the geochemical state of the deep ocean. Here we present a record that more directly reflects deep-ocean oxygen concentrations, based on the ratio of Fe3+ to total Fe in hydrothermally altered basalts formed in ocean basins. Our data allow for quantitative estimates of deep-ocean dissolved oxygen concentrations from 3.5 billion years ago to 14 million years ago and suggest that deep-ocean oxygenation occurred in the Phanerozoic (541 million years ago to the present) and potentially not until the late Palaeozoic (less than 420 million years ago).

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Figure 1: Average Fe3+/ΣFe ratios of basalts from specific ophiolites and drilled oceanic crust.
Figure 2: Histograms of Fe3+/ΣFe ratios from individual samples as a function of time period.
Figure 3: Comparison of Fe3+/ΣFe ratios from ophiolite basalts versus continental volcanic rocks (including subaerial volcanics).
Figure 4: Calculated deep-ocean O2 concentrations versus time compared to previous estimates of 𝑝O2,atm.

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Acknowledgements

D.A.S. acknowledges discussions with M. Bender, B. Buffett, D. DePaolo, J. Eiler, S. Finnegan, W. Fischer, J. Higgins, A. Saal and E. Stolper. We thank D. Canfield for advice on a prior draft. C.B.K. acknowledges support from the Ann and Gordon Getty Foundation.

Author information

Authors and Affiliations

  1. Department of Earth and Planetary Science, University of California, Berkeley, 94720, California, USA

    Daniel A. Stolper & C. Brenhin Keller

  2. Berkeley Geochronology Center, Berkeley, 94720, California, USA

    C. Brenhin Keller

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Contributions

D.A.S. conceived the study and compiled the ophiolite basalt data. C.B.K. provided the continental volcanic data. Both authors contributed to data analysis, modelling and writing.

Corresponding author

Correspondence to Daniel A. Stolper.

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The authors declare no competing financial interests.

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Reviewer Information Nature thanks L. Kump and E. Sperling for their contribution to the peer review of this work.

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Extended data figures and tables

Extended Data Figure 1 Relationships between Fe3+/ΣFe, total iron, and sample age.

a, Fe3+/ΣFe versus total Fe for all ophiolite basalt data. The regression line (dotted grey line) is a linear regression through all data with a 95% confidence interval shaded in grey. b, Total Fe versus age for all ophiolite data. The regression line (dotted grey line) is a linear regression through all data with a 95% confidence interval shaded in grey. Combination of the regression lines in a and b indicates a maximum shift in Fe3+/ΣFe ratios over the past 3.5 billion years of 0.04 ± 0.03 (2σ).

Extended Data Figure 2 Fe3+/ΣFe versus total Fe for Precambrian ophiolite basalts.

The regression line (dotted grey line) is a linear regression through Precambrian ophiolite basalts with a 95% confidence interval shaded in grey. The slope is not distinguishable from 0 at the 2σ level. If secondary metamorphic reduction occurred in these samples, we would expect samples with less Fe to be consistently lower in Fe3+/ΣFe ratios than samples with more Fe. This is not observed, indicating that such metamorphic reduction has not obviously affected the Fe3+/ΣFe ratios of samples.

Extended Data Table 1 Tukey–HSD pairwise comparison test of average mean ophiolite Fe3+/ΣFe ratios for the given age bins
Full size table
Extended Data Table 2 Wilcoxon pairwise comparison test (with Holm P-adjustment correction) of average mean ophiolite Fe3+/ΣFe ratios for the given age bins
Full size table

Supplementary information

Supplementary Table 1

This file contains compiled data from ophiolite basalts. (XLSX 229 kb)

Supplementary Table 2

This file contains compiled data from drilled oceanic crust. (XLSX 126 kb)

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Stolper, D., Keller, C. A record of deep-ocean dissolved O2 from the oxidation state of iron in submarine basalts. Nature 553, 323–327 (2018). https://doi.org/10.1038/nature25009

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